JP2018524418A - Polyurethane coating composition - Google Patents

Abstract

  The present invention relates to at least one polyol (A), at least one silane-modified compound (B) of the formula (I) and optionally one or more silanes having free isocyanate groups or blocked isocyanate groups The present invention relates to a non-aqueous coating agent composition comprising an aliphatic or cycloaliphatic polyisocyanate (C) free from silane and at least one catalyst (D) for crosslinking of silane groups. Furthermore, the non-aqueous coating agent composition according to the present invention may contain one or more surface additives (E) and one or more non-aqueous solvents (F).

Description

  The present invention relates to at least one polyol (A), at least one silane-modified compound (B) of the formula (I) and optionally one or more silanes having free isocyanate groups or blocked isocyanate groups A non-aqueous coating material composition comprising an aliphatic or cycloaliphatic polyisocyanate (C) free of silane and at least one catalyst (D) for crosslinking of silane groups, comprising two components (B) And at least one of (C) relates to a composition that necessarily contains free or blocked isocyanate groups. The non-aqueous coating material composition of the present invention may further include one or more surface additives (E) and a solvent (F). The coating aids according to the invention are particularly suitable for automotive paints, in particular for the first automotive finishes (known as OEM coatings).

  Two-part polyurethane (PU) coating materials are used for overcoating in the automotive industry due to environmental effects, particularly high resistance to acid rain, compared to conventional coating systems crosslinked with amino resins (W. Wieczorerk in: Stoy / Freitag, Lackharze [resins for coatings], p. 215ff, C. Hanser-Verlag, 1996; J. W. Holubka et al., J. Coat. .77, 2000). Here, polyisocyanates based on OH-functional poly (meth) acrylate resins and hexamethylene diisocyanate (HDI) are generally used. The use of other diisocyanates or other diisocyanate derivatives is possible as well.

  Over the years, efforts have been made to develop new automotive clearcoat materials. In view of the growing quality requirements in the automotive industry, efforts are being made to improve resistance to environmental impacts in particular and high mechanical stability, in particular scratch resistance.

  One possibility to improve the scratch resistance of a two-part polyurethane coating is to introduce trialkoxysilane groups into the coating component. These silane components can increase the stability of the polyurethane coating by crosslinking and forming the siloxane network. This principle is taught by EP 1273640. This publication describes a polyol component and an aliphatic and / or cycloaliphatic polyisocyanate or polymerized, allophanated, biuretized, in which 0.1 to 95 mol% of the free isocyanate groups initially present are reacted with bisalkoxysilylamines. Alternatively, a two-component (2K) coating material is described that includes a crosslinker component comprising a polyisocyanate derived therefrom by urethanization. These coating materials can be used to produce clear coats or top finishes in the automotive segment, and after complete cure, exhibit good scratch resistance combined with good resistance to environmental effects. However, the visual impression given by the sandability and polish and the resulting coating can still be improved further.

  The principle of polyurethane coatings comprising polyisocyanate compounds that react proportionally with isocyanate groups to form silane groups has been continually explored in recent years-in particular, patent applications WO 2007/033786, WO 2008. Compare US Pat. No. 7,74489, WO 2009/077181, US 2011/0269897, WO 2012/168079, and WO 2014/086530. These texts describe various alkoxysilane-containing polyisocyanates as components for crosslinking with polyols. Various monoaminosilane, bisaminosilane and mercaptosilane components and mixtures thereof are also used for reaction with polyisocyanates. In addition to the use of various silane components, new catalysts have also been described for improved crosslinking of the silane structure.

  The second approach relates to improving the scratch resistance of two-part polyurethane coatings by adding an isocyanate-free silane-terminated prepolymer. This type of approach is described, for example, in patent applications, EP 2676982 and EP 2735578.

  In view of the ever-increasing quality requirements imposed on automotive clearcoats, the need for new components to produce such coating formulations continues to exist.

  Very generally, the silane-modified compounds of the type claimed here contain silane groups with hydrolyzable groups, and the polymer backbone is substantially O-Si-O-Si chains as in the case of silicones. Instead, it is instead a compound constructed from a C-C chain, which in most cases is interrupted by heteroatoms and further contains urethanes, ethers, esters, ureas, amides and other structural units. Upon exposure to moisture and / or under the influence of a suitable catalyst, groups on the silane group (usually acetate groups or alkoxy groups, for example) are hydrolyzed to form reactive silanols, which are then condensed and cured. To form a high molecular mass network, in which water, alcohol or acetic acid is excluded.

  Compositions containing silane-modified compounds are notable for quality that includes a high level of adhesion to any of a very wide variety of substrates without expensive and inconvenient pretreatment (no need for a primer). This is because OH groups are usually present on the inorganic substrate surface and can react with the reactive silanols of the polymer formed upon exposure to moisture.

Silane modified polyurethanes and polyureas currently on the market are represented by the following formula scheme: (i) by reaction of NCO-containing prepolymer with aminosilane or (ii) OH-terminated prepolymer (polyether, polyurethane) Or polyester, etc.) with, for example, an NCO functional silane or (iii) a high molecular mass backbone generated by the reaction of an NCO-containing prepolymer with a mercaptosilane.

Furthermore, as already mentioned, the hardness of the resulting coating as the final product after silane crosslinking is very important for automotive paints. In the case of silane-modified polyurea, the final product usually has a high hardness. However, perhaps the coating is very hard and highly crosslinked, which can cause cracks. In contrast, silane modified polyurethanes provide a softer final product after curing. Nevertheless, the synthesis of silane-modified polyurethanes with high silane content is difficult to carry out economically because of the relatively expensive NCO-functionalized silane precursors.

EP 1273640 International Publication No. 2007/033786 Pamphlet International Publication No. 2008/74489 Pamphlet International Publication No. 2009/077181 Pamphlet US Patent Application Publication No. 2011/0269897 International Publication No. 2012/168079 Pamphlet International Publication No. 2014/085530 Pamphlet European Patent No. 2,676,982 European Patent No. 2735578

W. Wieczorerk in: Stoy / Freitag, Lackharze [resins for coatings], p. 215ff, C.I. Hanser-Verlag, 1996 J. et al. W. Holubka et al. , J .; Coat. Tech. Vol. 72, no. 901, p. 77,2000

  The problem to be solved by the present invention is to provide an improved non-aqueous coating system comprised of cheap and readily available starting materials. This object relates in particular to a non-aqueous coating material composition having an advantageous balance of chemical properties, in particular the degree of cure and stability, and having the excellent performance characteristics of automotive paints.

  The subject of the present invention is a non-aqueous coating material composition as described in one or more preferred embodiments as described in claim 1 or in the dependent claims or in the following description. Further subjects of the present invention are multi-step coating methods using these coating material compositions, and the use of the coating material composition as a clearcoat or topcoat material, and OEM finishing of automobiles and / or utility vehicles, respectively. Application of coating method for.

  Surprisingly, it has been found that the coating material composition of the present invention results in a coating having a characteristic profile that makes the coating particularly suitable for automotive paints. This property profile includes good processing quality during compounding as well as a high degree of wet and dry scratch resistance after baking of the coating material, especially a significant retention of gloss after scratch exposure, but at the same time good Also included are solvent resistance and low pendulum damping. The resulting coating exhibits a very good visual impression overall.

Definitions As used in this application, the term “aliphatic” may mean that a non-adjacent methylene group (—CH ₂ —) may be replaced, in particular, by a heteroatom such as oxygen and sulfur, or by a secondary amino group. Represents an optionally substituted linear or branched alkyl, alkenyl and alkynyl group.

  As used in this application, the term “alicyclic” or “cycloaliphatic” refers to an optionally substituted carbocyclic or heterocyclic compound not included in an aromatic compound, such as cycloalkane, cycloalkene or Represents oxa-, thia-, aza- or thiazacycloalkane. Specific examples thereof are cyclohexyl groups, cyclopentyl groups and derivatives thereof interrupted by one or two N or O atoms, such as pyrimidine, pyrazine, tetrahydropyran or tetrahydrofuran. Further examples of alicyclic groups include rings such as iminooxadiazinedione, oxadiazinetrione, oxazolidinone, allophanate, cyclic isocyanurate, cyclic uretdione, cyclic urethane, cyclic biuret, cyclic urea, acylurea and / or carbodiimide structures. A polyisocyanate having a structure.

As used in this application, the term “optionally substituted” or “substituted” refers to the related structural units —F, —Cl, —I, —Br, —OH, —OCH ₃ , -OCH ₂ CH _3, -O- isopropyl or _{-O-n-propyl, -OCF 3, -CF 3, -S} -C 1~6 - having an alkyl and / or 1 to 12 carbon atoms, a hetero It represents in particular a substitution with another linear or branched, aliphatic and / or alicyclic structural unit which may be linked via an atom. This preferably represents substitution by halogen (especially -F, -Cl), _C1-6 -alkoxy (especially methoxy and ethoxy), hydroxyl, trifluoromethyl and trifluoromethoxy.

As used in this application, the term “low molecular mass” refers to a compound whose molecular mass is up to 800 g · mol ⁻¹ .

As used in this application, the term “polymer mass” refers to a compound whose molecular mass exceeds 800 g · mol ⁻¹ .

  For example, in the case of compounds whose molecular mass does not arise from a precisely defined structural formula, as in the case of polymers, the molecular mass refers in each case to the number average molecular weight.

  As used in this application, the term “polyisocyanate” refers to aliphatic or cycloaliphatic polyisocyanates having an NCO functionality of more than 1, preferably 2 or more, in particular di- and triisocyanates.

  As used in this application, the term “monomer” refers to a low molecular weight compound having a functional group with a given molar mass that participates in the synthesis of oligomers and / or (pre) polymers.

  As used in this application, the term “oligomer” refers to a compound in which a very small number (ie 10 or fewer) of the same or different types are repeatedly linked together.

  As used in this application, the term “prepolymer” refers to an oligomeric compound having functional groups that participate in the final composition of the polymer. In particular, this includes compounds which contain at least one diisocyanate unit and at least one diol unit, as usual in polyurethane chemistry, and which can be polymerized via the functional groups of these units.

  As used in this application, the term “polymer” means that the same or different types of monomers, oligomers and / or prepolymers are repeatedly linked to each other in terms of degree of polymerization, molar mass distribution and / or chain length. Represents a polymeric mass unit that may be different.

  In this application, the term “compound” also encompasses oligomers and prepolymers.

  For the purposes of this application, the term “blocked” indicates “reversibly blocked”. Thus, for example, isocyanate can be released again from blocked isocyanate groups by heating; therefore, the blocked isocyanate groups remain reactive with the polyol. Blocked isocyanates are typically understood as adducts of highly reactive isocyanates with alcohols (forming urethanes) or amines (forming urea), again at high temperatures, again with alcohols or amines, and isocyanates, respectively. Disassembled into Known blocking agents are, for example, acetoacetic acid, malonic esters, 3,5-dimethylpyrazole, butanone oxime, secondary amines, caprolactam or various alcohols.

  Unless otherwise indicated by the context, the term “isocyanate group” in this application always encompasses free isocyanate groups (—NCO) and blocked isocyanate groups.

As used in this application, the secondary “formamidosilane” has the following structural formula:

Wherein R ¹ , R ² , R ³ and n are as defined in claim 1
It is a compound of this. Thus, a “formamidosilane group” is generally represented as follows:

(Wherein R ¹ , R ² , R ³ and n are as defined in claim 1).

  When the nitrogen atom is substituted by 3 carbon atoms, the term “tertiary formamidosilane” or “tertiary formamidosilane group” is used. Correspondingly, when the nitrogen atom is replaced by two carbon atoms, a secondary formamidosilane or a secondary formamidosilane group is mentioned.

  The present invention comprises at least one polyhydroxyl group-containing compound (A), at least one silane-modified compound B of formula (I) as defined in claim 1 and optionally free isocyanate groups or blocked isocyanates. A non-aqueous coating material composition comprising one or more silane-free aliphatic or cycloaliphatic polyisocyanates (C) having a group and at least one catalyst (D) for crosslinking of the silane groups . Furthermore, the non-aqueous coating material composition of the present invention can comprise one or more rheology aids (E) and one or more non-aqueous solvents (F). The non-aqueous coating material composition of the present invention can include the additional components shown below. However, in one preferred embodiment, the non-aqueous coating material composition is from components (A)-(F) or sub-loops thereof only, for example from (A), (B), (C) and (D), (A ), (B), (C), (D) and (E) to (A), (B), (D), (E) and (F) to (A), (B), (D ) And (E) or only (A), (B) and (D).

  In the coating material composition of the present invention, at least one of the two components (B) and (C) must contain free isocyanate groups or blocked isocyanate groups. Therefore, if the composition does not contain component (C), component (B) must be selected so that it still has isocyanate groups that subsequently undergo crosslinking with polyol component (A).

  The ingredients are described in detail below.

Component (A) -Polyol As an essential component (A), the coating material composition of the present invention first contains a compound having two or more hydroxyl groups (in the literature, also called a polyhydroxyl group-containing compound or abbreviated as a polyol). .

  Examples of suitable oligomeric or polymeric compounds which contain at least one, in particular at least two (one or more) isocyanate-reactive hydroxy functions and can be used as component (A) in the present invention are linear And / or branched and / or blockwise, comb and / or randomly structured oligomers or polymers, such as (meth) acrylate (co) polymers, polyesters, alkyds, amino resins, polyurethanes, polylactones, polycarbonates, poly Ethers, epoxy resin-amine adducts, (meth) acrylate diols, partially hydrolyzed polyvinyl esters or polyureas, among which (meth) acrylate copolymers, polyesters, polyurethanes, polyethers. And epoxy resin - amine adducts, especially the (meth) acrylate (co) polymers and polyesters are preferred.

Component A preferably comprises at least one hydroxy functional polyester (or polyester polyol) having a hydroxyl number of 20 to 240 mg KOH / g, preferably 30 to 200 mg KOH / g, more preferably 40 to 160 mg KOH / g. The acid value is less than 20 mgKOH / g, preferably less than 15 mgKOH / g, more preferably less than 12 mgKOH / g. The glass transition temperature of component A is −40 to + 100 ° C., preferably 30 to + 80 ° C., more preferably −30 to + 70 ° C. The molecular weight of the polyester polyol as calculated from the stoichiometry of the starting materials used is about 460-11300 g / mol, preferably about 570-7500 g / mol, more preferably about 700-5700 g / mol. In preparing the hydroxy functional polyester, a total of 6 monomer component groups can be used:
1) (Cyclo) alkanediols (ie dihydric alcohols having a hydroxyl group attached to a (cyclo) aliphatic), such as ethanediol, 1,2- and 1,3-propane, with a molecular weight range of 62-286 g / mol Diol, 1,2-, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, cyclohexane-1,4-dimethanol, 1,2- And 1,4-cyclohexanediol, 2-ethyl-2-butylpropanediol, diols containing ether oxygen, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, about 2000 g / mol, preferably Is about 1000 g / mol, Ri is preferably polyethylene, polypropylene or polybutylene glycols having a maximum molecular weight of about 500 g / mol. The reaction product of the diol and ε-caprolactone can also be used as the diol.

  2) Alcohols having a functionality of 3 or higher and a molecular weight range of 92-254 g / mol, such as glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.

  3) Monoalcohols such as ethanol, 1- and 2-propanol, 1- and 2-butanol, 1-hexanol, 2-ethylhexanol, cyclohexanol and benzyl alcohol.

  4) Dicarboxylic acid having a molecular weight range of 116 to about 600 g / mol and / or its anhydride, such as phthalic acid, phthalic anhydride, isophthalic acid, tetrahydrophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic acid, hexahydrophthalic acid Anhydride, maleic anhydride, fumaric acid, succinic acid, succinic anhydride, adipic acid, dodecanedioic acid, hydrogenated dimer fatty acid.

  5) Higher polyfunctional carboxylic acids and / or their anhydrides, such as trimellitic acid and trimellitic anhydride.

  6) Monocarboxylic acids such as benzoic acid, cyclohexanecarboxylic acid, 2-ethylhexanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, natural and synthetic fatty acids.

  A more preferred hydroxy functional component is a (meth) acrylate copolymer.

Particularly suitable (meth) acrylate copolymers are
An OH number of −100 to 220, preferably 130 to 200, more preferably 140 to 190, in particular 145 to 180 mg KOH / g,
A glass transition temperature of −35 to + 60 ° C., in particular −25 to + 40 ° C.
It has a number average molecular weight of -1000 to 10000 daltons, in particular 1500 to 5000 daltons, and a mass average molecular weight of -2000 to 40000 daltons, in particular 3000 to 20000 daltons.

(Meth) acrylate copolymer
(A1) in each case based on hydroxyl group-containing monomer (a) 20-90% by weight, preferably 22-85% by weight, more preferably 25-80% by weight, in particular 28-75% by weight of 4-hydroxy Selected from the group consisting of butyl (meth) acrylate and 2-alkylpropane-1,3-diol mono (meth) acrylate,
(A2) In each case, based on the hydroxyl group-containing monomer (a), 20 to 80% by weight, preferably 15 to 78% by weight, more preferably 20 to 75% by weight, especially 25 to 72% by weight of other hydroxyl groups Selected from the group consisting of group-containing olefinically unsaturated monomers,
A hydroxyl group-containing olefinically unsaturated monomer (a) corresponding to the OH value is contained in a copolymerized form.

  Examples of suitable 2-alkylpropane-1,3-diol-mono (meth) acrylates (a1) are 2-methyl-, 2-ethyl-, 2-propyl-, 2-isopropyl- or 2-n-butyl. Propane-1,3-diol mono (meth) acrylate, and 2-methylpropane-1,3-diol-mono (meth) acrylate is particularly advantageous and is preferably used.

  Examples of suitable other hydroxyl group-containing olefinically unsaturated monomers (a2) are olefinically unsaturated carboxylic acids, hydroxyalkyl esters of sulfonic and phosphonic acids, and acidic phosphoric and sulfuric esters, in particular carboxylic acids such as acrylics. Acids, β-carboxyethyl acrylate, methacrylic acid, ethacrylic acid and crotonic acid, in particular acrylic acid and methacrylic acid. These are derived from alkylene glycols esterified with acids or can be obtained by reaction of acids with alkylene oxides such as ethylene oxide or propylene oxide. Preferably used hydroxyalkyl esters are those in which the hydroxyalkyl group contains up to 20 carbon atoms, in particular 2-hydroxyethyl or 3-hydroxypropyl acrylate or methacrylate; 1A-bis (hydroxymethyl) cyclohexane- or octahydro- 4,7-methano-1H-indene-dimethanol monoacrylate or monomethacrylate; or a reaction product of a cyclic ester such as ε-caprolactone and its hydroxyalkyl ester; or an olefinically unsaturated alcohol such as allyl alcohol; or a polyol, For example, trimethylolpropane monoallyl or diallyl ether or pentaerythritol monoallyl, diallyl or triallyl ether

  These more highly multifunctional monomers (a2) are generally used only in small amounts. In the context of the present invention, the “small amount” of the more highly multifunctional monomer (a2) here refers to the crosslinking of (meth) acrylate copolymer A, unless it is intended to be in the form of crosslinked microgel particles. Refers to an amount that does not cause gelation.

  Further contemplated as monomer (a2) are ethoxylated and / or propoxylated allyl alcohols or 2-hydroxyalkyl allyl ethers, in particular 2-hydroxyethyl allyl ether sold by Arco Chemicals. If used, these are preferably not used as single monomers (a2) but instead in amounts of 0.1 to 10% by weight, based on the (meth) acrylate copolymer.

  Furthermore, with the above olefinically unsaturated acids, in particular acrylic acid and / or methacrylic acid, and α-branched monocarboxylic acids having 5 to 18 carbon atoms per molecule, in particular Versatic® acid glycidyl esters. Reaction product, or instead of the reaction product, then during or after the polymerization reaction, an α-branched monocarboxylic acid having 5 to 18 carbons per molecule, in particular Versatic® acid glycidyl ester Equal amounts of the above olefinically unsaturated acids, especially acrylic acid and / or methacrylic acid, which can be reacted with are contemplated (Rompp Lexikon Racke und Druckfarben, George Thieme Verlag, Stuttgart, New York, 1998, “Versati. (Registered trademark) acids ", see pages 605 and 606).

  Reaction of hydroxy functional silane with epichlorohydrin and subsequent reaction products with (meth) acrylic acid and / or hydroxyalkyl and / or hydroxycycloalkyl esters of (meth) acrylic acid and / or further hydroxyl group-containing monomers Particularly suitable are acryloyloxysilane-containing vinyl monomers as monomers (a2) which can be prepared by the reaction of (a1) and (a2).

  Apart from hydroxyl groups, the (meth) acrylate copolymers may contain other isocyanate-reactive functional groups such as primary and secondary amino groups.

  Apart from the isocyanate-reactive functional groups, the (meth) acrylate copolymers contain small amounts of further heat-activatable reactive functional groups such as carboxyl groups, methylol ether groups, epoxide groups and / or blocked isocyanate groups. May be.

Examples of suitable olefinically unsaturated monomers (a3) that can be used to introduce isocyanate-reactive amino groups and additional heat-activatable reactive functional groups into (meth) acrylate copolymers are:
(A31) monomers having at least one amino group per molecule, such as aminoethyl acrylate, aminoethyl methacrylate, allylamine or N-methylaminoethyl acrylate;
And / or (a32) monomers having at least one acid group per molecule, such as acrylic acid, β-carboxyethyl acrylate, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid; Saturated sulfone or phosphonic acid or partial esters thereof; mono (meth) acryloyloxyethyl maleate, mono (meth) acryloyloxyethyl succinate, mono (meth) acryloyloxyethyl phthalate; or vinyl benzoic acid and methyl vinyl benzoic acid , And vinylbenzenesulfonic acid (all isomers in each case);
(A33) A monomer containing an epoxide group, such as glycidyl ester of acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, maleic acid, fumaric acid or itaconic acid, or allyl glycidyl ether.

Furthermore, the (meth) acrylate copolymer may contain at least one olefinically unsaturated monomer (a4) in copolymerized form substantially or completely free of reactive functional groups, for example:
Monomer (a41):
(Meth) acrylic acid esters substantially free of acid groups, such as alkyl groups, in particular methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, hexyl, ethylhexyl, stearyl and lauryl acrylate or methacrylate Alkyl or cycloalkyl esters of (meth) acrylic acid having up to 20 carbon atoms; cycloaliphatic (meth) acrylic esters, in particular cyclohexyl, isobornyl, dicyclopentadienyl, octahydro-4,7-methano- 1H-indenemethanol or tert-butylcyclohexyl (meth) acrylate; oxaalkyl or oxacycloalkyl esters of (meth) acrylic acid such as ethoxytriglycol (meth) acrylate and preferably 550 / Mol methoxy oligo glycol (meth) acrylate having a molecular weight M _n of or free of other ethoxylated and / or propoxylated hydroxyl groups, (meth) acrylic acid derivative (This kind of suitable monomers (31) Further examples of this are known from published specification DE 19625773, 3rd, 65th to 4th, 20th line). These are small amounts of highly functional alkyl (meth) acrylates or cycloalkyl esters such as ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butylene glycol, pentane-1,5-diol, hexane-1,6. -Diol, octahydro-4,7-methano-1H-indenedimethanol or cyclohexane-1,2-, -1,3- or -1,4-diol di (meth) acrylate; trimethylolpropane di- or tri (meth) ) Acrylates; or pentaerythritol di-, tri- or tetra (meth) acrylates. Here, a minor amount of the polyfunctional monomer (a41) means an amount that does not cause crosslinking or gelation of the copolymer unless it is in the form of crosslinked microgel particles.

Monomer (a42):
Vinyl ester of α-branched monocarboxylic acid having 5 to 18 carbons in the molecule. Branched monocarboxylic acids can be obtained by reacting formic acid or carbon monoxide and water with olefins in the presence of a liquid strongly acidic catalyst. The olefin may be a cracked product of paraffinic hydrocarbons such as mineral oil fractions and may include not only branched but also straight chain acyclic and / or cycloaliphatic olefins. Such a reaction of olefins with formic acid or carbon monoxide and water forms a mixture of carboxylic acids in which the carboxyl groups are mainly located on quaternary carbon atoms. Other olefin starting materials are, for example, propylene trimer, propylene tetramer and diisobutylene. Alternatively, the vinyl ester can be prepared in a conventional manner from an acid, for example by reacting the acid with acetylene.

  Vinyl esters of saturated aliphatic monocarboxylic acids having 9 to 11 carbons branched on the α carbon are particularly preferred because they are readily available. This type of vinyl ester is sold under the trade name VeoVa (R) (see also Rompp Lexikon Rack Druckfarben, George Thime Verlag, Stuttgart, New York, 1998, page 598).

Monomer (a43):
Nitriles such as acrylonitrile and / or methacrylonitrile.

Monomer (a44):
Vinyl compounds, in particular vinyl halides and / or vinylidene dihalides, such as vinyl chloride, vinyl fluoride, vinylidene dichloride or vinylidene difluoride; N-vinylamides, such as vinyl-N-methylformamide, N-vinylcaprolactam or N- 1-vinylimidazole; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether and / or vinyl cyclohexyl ether; and / or vinyl esters such as vinyl acetate, vinyl propionate, Vinyl esters of vinyl butyrate, vinyl pivalate and / or 2-methyl-2-ethylheptanoic acid.

Monomer (a45):
Allyl compounds, in particular allyl ethers and allyl esters, such as allyl methyl, ethyl, propyl or butyl ether or allyl acetate, propionate or butyrate.

Monomer (a46):
German Patent 3,807,571, pages 5-7, German Patent 3,706,095, 3-7, European Patent 0358153, pages 3-6, US Pat. No. 4,754,914, 5-9 No. 4,421,823 or International Patent Application Publication No. 1992/22615, page 12, line 18 to page 18, line 10 and a number average molecular weight of 1000 to 40000 g / mol per molecule. Polysiloxane macromonomer having Mn and an average of 0.5 to 2.5 ethylenically unsaturated double bonds; especially 2000 to 20000 g / mol, more preferably 2500 to 10000 g / mol, in particular 3000 to 7000 g / mol per molecule. mol number average molecular weight _Mn and average 0.5-2.5, preferably 0.5-1. A polysiloxane macromonomer having 5 ethylenically unsaturated double bonds.

Monomers (a1) and (a2) and (a3) and / or (a4) are selected such that the above OH number and glass transition temperature occur. The selection of monomer (a) to establish the glass transition temperature is made by one skilled in the art using the following Fox equation that can be used to approximately calculate the glass transition temperature of poly (meth) acrylates: be able to:
n = x
1 / Tg = ΣW _n / Tg _n ; Σ _n W _n = 1 n = 1
Tg = glass transition temperature of poly (meth) acrylate;
W _n = weight fraction of the n th monomer;
Tg _n = glass transition temperature of the nth homopolymer monomer and x = number of different monomers.

  The preparation of (meth) acrylate copolymers preferably used in the present invention does not have procedure specialities, instead, preferably at temperatures of 50-200 ° C., stirred tanks, autoclaves, tubular reactors, loop-type reactions In a reactor or Taylor reactor under atmospheric or superatmospheric pressure, using continuous or batch, radical-initiated copolymerization in bulk, solutions, emulsions, miniemulsions or microemulsions using methods known and known in the polymer field .

  Examples of suitable copolymerization methods are published applications DE 19709465, DE 19709476, DE 2848906, DE 19524182, DE 19828742. Specification, German Patent No. 19628143, German Patent No. 19628142, European Patent No. 05574783, International Publication No. 1995/27742, International Publication No. WO02 / 02387 or International Publication No. 1998. / 02466 pamphlet. Alternatively, the copolymerization can also be carried out in a polyol as the reaction medium, as described, for example, in German patent application DE 1850243, which is a German patent application. Examples of suitable radical initiators include dialkyl peroxides such as di-tert-butyl peroxide or dicumyl peroxide; hydroperoxides such as cumene hydroperoxide or tert-butyl hydroperoxide; peresters such as tert-butyl perbenzoate, tert Butyl perpivalate, tert-butyl per-3,5,5-trimethylhexanoate or tert-butyl per-2-ethylhexanoate; peroxodicarbonate; potassium, sodium or ammonium peroxodisulfate; azo initiators such as Azodinitriles such as azobisisobutyronitrile; C—C cleavage initiators such as benzopinacol silyl ethers; or a combination of a non-oxidizing initiator and hydrogen peroxide A. Combinations of the above initiators can also be used.

  Further examples of suitable initiators are described in German patent application DE 19628142, page 3, line 49 to page 4, line 6. A relatively large amount of radical initiator is preferably added, the proportion of initiator in the reaction mixture being in each case based on the total amount of monomer (a) and initiator, more preferably 0.2 to 20% by weight, It is preferably 0.5 to 15% by weight, particularly 1.0 to 10% by weight.

  Furthermore, thiocarbonylthio compounds or mercaptans such as dodecyl mercaptan can be used as chain transfer agents or molecular weight regulators.

  For example, Setulx 1774 SS-65, Setalx D A 665 BA, Setalx D A 870 BA, Setalx D A 365 BA / X, Setlux D A HS 1170 BA, and Setlux BA AX 7 from Nuplex are suitable.

  Aliphatic polycarbonate polyols are also contemplated for the synthesis of the prepolymers of the present invention. Polycarbonate polyols can be obtained, as is known, from condensation reactions of phosgene and polyols or transesterification reactions of suitable organic carbonates and polyols. Organic carbonates contemplated include alkyl and alkylene carbonates and mixtures thereof. Examples include dimethyl carbonate (DMC), diethyl carbonate (DEC) and ethylene carbonate. The polyols contemplated are those polyols described above in the section on polyester polyols. The functionality of the polycarbonate polyol used is preferably 1.6 to 3.8, more preferably 1.8 to 3.5. These polycarbonate polyols preferably have a number average molecular weight of 100 to 6000 g / mol, more preferably 100 to 4000 g / mol. The OH number depends on the functionality of the polycarbonate polyol and is typically 20-900 mg KOH / g.

  Further suitable polyols are, for example, those described in EP 0 695 556 and EP 0 937 110, for example by reaction of epoxidized fatty acid esters with aliphatic or aromatic polyols. It is a specific polyol obtained by opening.

  Polybutadienes containing hydroxyl groups can serve as polyols as well.

Component B
As an essential component (B), the coating material composition according to the invention comprises at least one silane-modified compound of formula (I), in particular a compound of formula (II), as defined in the claims in each case. Hereinafter, such compounds of formula (I) or (II) are abbreviated as STP based on their silane modification (especially silane termination). In the final fully cured state, the present invention provides a polyurethane (PU) polymer condensed via -Si-O-Si-crosslinks as a permanent coating.

Component (B) used according to the present invention has the formula (I):
Formula (I)

(In the formula (I):
X is an organic molecular residue, in particular an optionally substituted, linear or branched, aliphatic or cycloaliphatic organic molecular residue;
R ¹ is an at least divalent, optionally substituted, linear or branched, aliphatic and / or alicyclic structural unit having ¹ to 12 carbon atoms, one or more non- Adjacent methylene groups can be replaced in each case by O or S;
R ² and R 3 are each independently an optionally substituted, straight or branched, aliphatic and / or alicyclic group having 1 to 12 carbon atoms;
n is an integer of 0-2)
At least one silane-modified compound (that is, a compound containing a tertiary silane formamide group).

In particular, according to the invention, in one preferred embodiment, a compound of formula (II) is used as silane-modified component (B):
Formula (II):

(In the formula (II):
Z is a molecular residue consisting of (i) a polyisocyanate or (ii) an NCO-containing polyurethane prepolymer, and per molecule, at least one NCO group of the structure referred to in (i) or (ii) has the formula Modified with secondary formamide silane to form a compound of (II);
R ¹ , R ² , R ³ and n are as defined above).

The acyclic and / or aliphatic polyisocyanates which serve as the parent structure Z of the compound (B) containing polyisocyanate groups are preferably substituted or unsubstituted aliphatic polyisocyanates known per se. Examples of preferred polyisocyanates include tetramethylene 1,4-diisocyanate, pentane 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, ethylene diisocyanate, dodecane 1 , 12-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis (4-isocyanatocyclohexyl) methane (H ₁₂ MDI) and mixtures of the above polyisocyanates. More preferred polyisocyanate parent structures of component (B) are polyisocyanates derived from this type of acyclic aliphatic polyisocyanates by trimerization, dimerization, urethanization, biuretization, uretdionelation and / or allophanatization, In particular biuret dimers and / or allophanate dimers and / or isocyanurate trimers.

  In a further embodiment, the polyisocyanate parent structure of component (B) is a polyisocyanate prepolymer having urethane structural units obtained by reaction of a polyol with a stoichiometric excess of the acyclic and / or aliphatic polyisocyanate. is there. Such polyisocyanate prepolymers are described, for example, in US Pat. No. 4,598,131.

  The polyisocyanate for preparing the prepolymer may be the polyisocyanate described above.

The polymer polyol that can be used for the preparation of the prepolymer has a number average molecular weight M _n of 400 g / mol to 8000 g / mol, preferably 400 g / mol to 6000 g / mol, more preferably 400 g / mol to 3000 g / mol. . Their hydroxyl numbers are 22-400 mg KOH / g, preferably 30-300 mg KOH / g, more preferably 40-250 mg KOH / g, which are 1.5-6, preferably 1.7-5, more preferably Has an OH functionality of 2.0-5.

  Polyols for preparing the prepolymers are organic polyhydroxyl compounds known in the art of single or mixture polyurethane coatings, such as standard polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylates. Polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, phenol / formaldehyde resins. Polyester polyol, polyether polyol or polycarbonate polyol is preferred, and polyether polyol is particularly preferred.

  Polyether polyols include, for example, polycondensation products of styrene oxide, ethylene oxide, propylene oxide, tetrahydrofuran, butylene oxide, epichlorohydrin, and mixed addition and graft products thereof, and condensation of polyhydric alcohols or mixtures thereof. Mention may be made of the polyols obtained and those obtained by alkoxylation of polyhydric alcohols, amines and amino alcohols.

Suitable hydroxy-functional polyethers have an OH functionality of 1.5 to 6.0, preferably 1.8 to 3.0, an OH number of 50 to 700, preferably 100 to 600 mg KOH / g solids, and 106 Having a molecular weight M _{n of} ˜4000 g / mol, preferably 200-3500, for example of hydroxy-functional starting molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol, etc. Alkoxylation products or mixtures thereof and other hydroxy functional compounds including propylene oxide or butylene oxide. As the polyether component, polypropylene oxide polyol, polyethylene oxide polyol and polytetramethylene oxide polyol are preferable.

  Examples of polyester polyols having good compatibility include di- and optionally tri- and tetraols known per se and polycondensates of di- and optionally tri- and tetracarboxylic acids or hydroxycarboxylic acids or lactones. is there. Instead of the free polycarboxylic acid, it is also possible to use the corresponding polycarboxylic anhydrides or the corresponding polycarboxylic esters of lower alcohols in the preparation of the polyesters. Examples of suitable diols include ethylene glycol, butylene glycol, diethylene glycol, triethylene glycol, polyalkylene glycols such as polyethylene glycol, and propane-1,2-diol, propane-1,3-diol, butane-1,3. -Diol, butane-1,4-diol, hexane-1,6-diol and isomers, neopentyl glycol or hydroxypivalic acid neopentyl glycol ester, the latter three compounds being preferred. To achieve a functionality of less than 2, it is possible to use a proportion of a polyol having a functionality of 3, such as trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate. is there.

  Useful dicarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid , Fumaric acid, itaconic acid, malonic acid, suberic acid, 2-methylsuccinic acid, 3,3-diethylglutaric acid, and 2,2-dimethylsuccinic acid. If present, anhydrides of these acids can be used as well. As a result, for the purposes of the present invention, anhydrides are covered by the expression “acid”. As long as the average functionality of the polyol is 2 or more, it is also possible to use monocarboxylic acids such as benzoic acid and hexanecarboxylic acid. Saturated aliphatic or aromatic acids such as adipic acid or isophthalic acid are preferred. An example of a polycarboxylic acid for optional additional use in small amounts is trimellitic acid.

  Examples of hydroxycarboxylic acids that can be used as co-reactants in the preparation of polyester polyols having terminal hydroxyl groups include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid, and the like. Usable lactones include ε-caprolactone, butyrolactone and homologues.

  Polyester polyols based on butanediol and / or neopentyl glycol and / or hexanediol and / or ethylene glycol and / or diethylene glycol and adipic acid and / or phthalic acid and / or isophthalic acid are preferred. Polyester polyols based on butanediol and / or neopentyl glycol and / or hexanediol and adipic acid and / or phthalic acid are particularly preferred.

  Useful polycarbonate polyols can be obtained by reaction of carbonic acid derivatives such as diphenyl carbonate, dimethyl carbonate or phosgene with diols. Useful diols of this type include, for example, ethylene glycol, propane-1,2- and 1,3-diol, butane-1,3- and 1,4-diol, hexane-1,6-diol, octane- 1,8-diol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methylpropane-1,3-diol, 2,2,4-trimethylpentane-1,3-diol, dipropylene glycol, polypropylene Also included are glycol, dibutylene glycol, polybutylene glycol, bisphenol A, tetrabromobisphenol A, and lactone-modified diols. Preferably, the diol component is 40-100% by weight hexane-1,6-diol and / or hexanediol derivatives, preferably those having not only terminal OH groups but also ether or ester groups, for example 1 mol of hexanediol and at least It contains the product obtained by reaction of 1 mol, preferably 1-2 mol ε-caprolactone, or by etherification of hexanediol to give di- or trihexylene glycol with itself. It is also possible to use polyether polycarbonate polyols.

  Polycarbonate polyols based on dimethyl carbonate and hexanediol and / or butanediol and / or ε-caprolactone are preferred. Very particular preference is given to polycarbonate polyols based on dimethyl carbonate and hexanediol and / or ε-caprolactone.

  Instead of the polymer polyether, polyester or polycarbonate polyol, it is also possible to use low molecular weight polyols to prepare isocyanate-containing prepolymers. Suitable low molecular weight polyols are short chain aliphatic, araliphatic or cycloaliphatic diols or triols, ie those containing from 2 to 20 carbon atoms. Examples of diols include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,4-diol. , Neopentyl glycol, 2-ethyl-2-butylpropanediol, trimethylpentanediol, regioisomer diethyloctanediol, 1,3-butyleneglycol, cyclohexanediol, cyclohexane-1,4-dimethanol, hexane-1,6 -Diol, cyclohexane-1,2- and -1,4-diol, hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane), 2,2-dimethyl-3-hydroxypropyl 2,2- The There are chill-3-hydroxy propionate. Butane-1,4-diol, cyclohexane-1,4-dimethanol and hexane-1,6-diol are preferred. Examples of suitable triols are trimethylolethane, trimethylolpropane or glycerol, with trimethylolpropane being preferred.

  The polyols can be used alone or as a mixture.

  For both the polyisocyanate (i) as defined in claim 2 and the NCO-containing polyurethane prepolymer (ii), the NCO groups present are modified, in whole or in part, with (secondary) formamidosilanes of the formula (II) A compound can be obtained.

The compound of formula (II) containing a silaneformamide group has a number average molecular weight M _n of less than 10000 g / mol, preferably less than 6000 g / mol, more preferably less than 4000 g / mol.

The isocyanate group of the polyisocyanate (i) or the isocyanate group of the polyurethane prepolymer (ii) is reacted with a (secondary) formamide silane according to the following reaction formula:

Where Z, R ¹ , R ² , R ³ and n are as defined above.

  There are in principle two possible routes for the reaction of the (secondary) formamide silane and the isocyanate-containing prepolymer forming the polyurethane prepolymer (ii) as defined in claim 2. Initially, an isocyanate-containing prepolymer can be prepared from a polyisocyanate and a polyol. The remaining isocyanate can be reacted with (secondary) formamidosilane in the last step. Alternatively, the polyisocyanate can be first reacted with a (secondary) formamide silane and the remaining isocyanate is reacted with the polyol hydroxyl groups in a second step. Thereafter, the obtained polyurethane prepolymer (ii) may be purified by continuous distillation such as thin film distillation.

Component C-Polyisocyanate As a preferred further component, the coating material composition of the present invention comprises one or more silanes having free isocyanate groups or blocked isocyanate groups of the type commonly used in the coating industry. May contain no aliphatic or cycloaliphatic polyisocyanate (C).

  The polyisocyanate component (C) has a free isocyanate group or a blocked isocyanate group and can be used for this kind of acyclic aliphatic polyhydride by trimerization, dimerization, urethanization, biuretization, uretdioneization and / or allophanatization. Polyisocyanates having acyclic, aliphatic polyisocyanate parent structures and / or polyisocyanate parent structures derived from isocyanates.

The acyclic and / or aliphatic polyisocyanates which serve as the parent structure of the compound (C) containing polyisocyanate groups are preferably substituted or unsubstituted aliphatic polyisocyanates known per se. Examples of preferred polyisocyanates include tetramethylene 1,4-diisocyanate, pentane 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, ethylene diisocyanate, dodecane 1 , 12-diisocyanate, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI), bis (4-isocyanatocyclohexyl) methane (H ₁₂ MDI) and mixtures of the above polyisocyanates. Furthermore, the preferred polyisocyanate parent structure of component (C) is a polyisocyanate derived from this type of acyclic aliphatic polyisocyanate by trimerization, dimerization, urethanization, biuretization, uretdionelation and / or allophanatization. In particular biuret dimers and / or allophanate dimers and / or isocyanurate trimers. In a further embodiment, the polyisocyanate parent structure of component (C) is a polyisocyanate prepolymer having urethane structural units obtained by reaction of a polyol with a stoichiometric excess of the acyclic and / or aliphatic polyisocyanate. is there. Such polyisocyanate prepolymers are described, for example, in US Pat. No. 4,598,131.

  Particularly preferred polyisocyanate parent structures of component (C) are pentane 1,5-diisocyanate, hexamethylene diisocyanate and / or its biuret dimer and / or allophanate dimer and / or isocyanurate trimer and / or its Uretodione, as well as mixtures of the polyisocyanate parent structures mentioned.

  A particularly preferred polyisocyanate parent structure of component (C) is pentane 1,5-diisocyanate, hexamethylene diisocyanate and / or its isocyanurate trimer, which may be combined with its uretdione.

  Examples of such polyisocyanates are Desmodur® series polyisocyanate resins from Bayer Material Science AG, Leverkusen, DE. Preferably, for example, hexamethylene diisocyanate such as Desmodur® N3900 having an NCO functionality of 2.8 to 3.6 or Desmodur® N3300 having an NCO functionality of 2.8 to 4.5. It is possible to use low viscosity aliphatic polyisocyanate resins based on trimers. These polyisocyanates are optionally, for example, butyl acetate such as 10% butyl acetate (Desmodur® N3390) or such as 32% butyl acetate / solvent naphtha 100 (Desmodur® N 3368 BA / SN). May be used in a mixture with a suitable solvent such as a suitable solvent mixture. All Desmodur (R) products are available from Bayer MaterialScience AG, Leverkusen, DE.

Component D—Catalyst As a further essential component, the coating material composition of the present invention comprises a catalyst (or “curing agent” or “activator”) that accelerates the hydrolysis and condensation of the silanol groups of component (B). Such catalysts are known to those skilled in the art. For example, acids such as sulfuric acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, acetic acid, trifluoroacetic acid and dibutyl phosphate, 1,5-diazabicyclo [4.3.0] non-5-ene (DBN) and 1, Bases such as N-substituted amidines such as 5-diazabicyclo [5.4.0] undec-7-ene (DBU), such as tetraisopropyl titanate, tetrabutyl titanate, titanium (IV) acetylacetonate, aluminum tri- Metal salts and metal chelates such as sec-butyrate, aluminum acetylacetonate, aluminum triflate or tin triflate can also be used.

  A catalyst based on aluminum oxide can be used as well. One preferred catalyst is, for example, Nano-X GmbH, X-add® KR9006 from Saarbrucken. Another preferred catalyst may be selected from the group consisting of tetraalkylammonium salts of organic acids, in particular tetrabutylammonium benzoate.

  These catalysts are in an amount of 0.02 up to 5% by weight, preferably up to 2% by weight, more preferably 0.05 up to 1.5% by weight, based on the weight of the silane-modified formamide (B) used. Used in. Depending on the nature and amount of the catalyst used, the coating material composition of the present invention has a wide temperature range, for example -20 to 200 ° C, preferably 0 to 180 ° C, more preferably 20 to 160 ° C, very preferably. Can be cured at 100-150 ° C. (for automotive OEM finish) or 20-60 ° C. (for automotive repair). At higher temperatures, fewer catalysts can be used, but at lower temperatures, more and / or more active catalysts are required.

Component E—Surface Additives As a further preferred component, the coating material composition of the present invention may comprise one or more surface additives. Such additives can particularly act to improve the wettability of hydrophobic surfaces and as flow control agents. In the intended use of the present invention, siloxane is preferably used. One particularly preferred surface additive (flow control agent) is a polyether-modified polydimethylsiloxane such as, for example, Byk® 331 from Byk-Chemie GmbH, Wesel, DE. Furthermore, BYK (registered trademark) 306 or BYK (registered trademark) 141 manufactured by Byk GmbH, TegoGlide (registered trademark) 440 manufactured by Evonik Industries AG, Essen, DE or Bay trademark registered by OMG Borchers GmbH, Langenfeld, DE (registered trademark) Products such as OL 17 can be used.

Component F-Solvent As a further component, the coating material composition of the present invention can comprise one or more solvents. These are particularly useful for setting the viscosity of the coating material composition within a desired range. The solvent is generally an organic, anhydrous solvent that is compatible with the other components of the coating material composition of the present invention. Examples of such solvents are the solvent naphtha (SN), 1-methoxyprop-2-yl acetate (MPA), butyl acetate (BA) and mixtures of these solvents.

Other Additives In addition to components (A)-(F), the coating material composition of the present invention may contain additional components (for example, fillers, lubricants, depending on the intended use and specific chemistry). Water repellents, flame retardants, stabilizers, light stabilizers such as UV absorbers and sterically hindered amines (HALS), and antioxidants, and coating aids (eg, anti-settling agents, antifoaming agents) And / or wetting agents, flow control agents, reactive diluents, plasticizers, co-solvents and / or thickeners and pigments, dyes and / or matting agents). Light stabilizers and the use of various types are described in A.S. Valet, Lichtschutzmittel fur Racke, Vincentz Verlag, Hanover, 1996.

  Suitable fillers include, by way of example, precipitated silica and fumed silica.

Preferred Embodiments According to the Present Invention Preferred embodiments are described in detail below.

In one preferred embodiment, the STP used in the coating material composition of the present invention has the general formula (II):
(In the formula (II):

Z is a molecular residue consisting of (i) a polyisocyanate or (ii) an NCO-containing polyurethane prepolymer, and per molecule, at least one NCO group of the structure referred to in (i) or (ii) is Modified with a secondary formamidosilane to form a compound of formula (II);
R ¹ has 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and is at least divalent, optionally substituted, linear or branched An aliphatic and / or cycloaliphatic structural unit of which one or more non-adjacent methylene groups can in each case be replaced by O or S;
R ² and R ³ are, in each case, independently of one another, optionally substituted, straight-chain or branched, aliphatic and having 1 to 12, preferably 1, 2 or 3 carbon atoms. / Or an alicyclic group;
n is an integer of 0 to 2, especially 0)
Have

Polyisocyanate (i)
In one particularly preferred embodiment, the structural unit Z is a group derived from a polyisocyanate. Suitable polyisocyanates used are known per se to the person skilled in the art and are preferably aliphatic or cycloaliphatic polyisocyanates having an NCO functionality of 2 or more. They can also have a uretdione, urethane, allophanate, isocyanurate, iminooxadiazinedione and / or biuret structure.

  The above polyisocyanates are known per se to the person skilled in the art and are based on di- and / or triisocyanates having isocyanate groups bonded to aliphatic and / or cycloaliphatic, which have been produced using phosgene. Or whether it was produced by a phosgene-free process is not important. Examples of such di- and / or triisocyanates include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1 , 5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and / or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10 Diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis (isocyanatomethyl) cyclohexane, 1-isocyanato-3,3,5-trimethyl-5 Isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4′-diisocyanatodicyclohexylmethane (Desmodu (Registered trademark) W, Bayer AG, Leverkusen, DE), 4-isocyanatomethyloctane 1,8-diisocyanate (triisocyanatononane, TIN), diisocyanato-1,3-dimethylcyclohexane (H6XDI), 1-isocyanato- There are 1-methyl-3-isocyanatomethylcyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane, bis (isocyanatomethyl) norbornane, and any desired mixture of said compounds.

  Particularly preferably, the polyisocyanates here are 2.0 to 5.0, very preferably an average NCO functionality of 2.3 to 4.5 and preferably 5.0 to 50.0% by weight, more preferably Has an isocyanate group content of 5.0 to 30.0% by weight.

  Particularly preferably, the polyisocyanates of the above type are pentane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, isomeric bis- (4,4′-isocyanatocyclohexyl) methane, mixtures thereof, and uretdione diesters of these polyisocyanates. Based on trimer, isocyanurate trimer and iminooxadiazinedione trimer.

Silane-modified compounds of formula (II) (Z is derived from polyisocyanate (i)) can advantageously be prepared by the following two-step process:

First of all, preferably an excess of alkyl formate R′O—CHO is converted to an amine H ₂ N—R ¹ —Si (R ₂ ) _n (OR ₃ ) _3-n (R ′ is preferably 1 to 4 An alkyl group having a carbon atom, where R ¹ , R ² , R ³ and n are as defined above). Particularly preferred as alkyl formate R′O—CHO is methyl formate or ethyl formate. Preferably, 1 mol of amine is reacted with an excess of alkyl formate R′O—CHO 1.01-6 mol, more preferably 1.05-4 mol at the boiling temperature of ethyl formate. After completion of the reaction, excess alkyl formate R′O—CHO and the resulting alcohol R′—OH were distilled off by thin film distillation, and the resulting (secondary) formamidosilane OHC—HN—R ¹ —Si (R _{2) n} (an _{OR 3) 3-n} may be isolated by filtration.

  The (secondary) formamidosilane is then reacted with a polyisocyanate of the formula Z-NCO, preferably under inert conditions, at a temperature of 20-200 ° C, preferably 40-160 ° C. The two components are here in an equivalent ratio of isocyanate groups to formamide groups of at least 1:10 up to 40: 1, preferably 1: 5 up to 30: 1, very preferably 1: 2 up to 25: 1. used. The reaction can be carried out in solution or in bulk without solvent. Depending on the stoichiometry of the reaction, the (tertiary) product of formula (II) containing formamidosilane groups may still contain free isocyanate groups.

  The preparation of the compound of formula (II) wherein Z is (i) a polyisocyanate can be carried out without the use of a catalyst. However, a known catalyst may be added to accelerate the reaction. Examples include tertiary amines such as triethylamine, tributylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ′, N′-tetramethyldiaminodiethyl ether, bis (dimethylaminopropyl) urea, N-methyl or N-ethylmorpholine, N-cocomorpholine, N-cyclohexylmorpholine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, N , N, N ′, N′-tetramethyl-1,6-hexanediamine, pentamethyldiethylenetriamine, N-methylpiperidine, N-dimethylaminoethylpiperidine, N, N′-dimethylpiperazine, N-methyl-N′- Dimethylaminopiperazine, 1,2-dimethylimidazo 2-methylimidazole, N, N-dimethylimidazole-β-phenylethylamine, 1,4-diazabicyclo [2.2.2] octane (DABCO) and bis (N, N-dimethylaminoethyl) adipate, amidine, For example, 1,5-diazabicyclo [4.3.0] nonene (DBN), 1,8-diazabicyclo [5.4.0] undec-7-ene (DBU) and 2,3-dimethyl-3,4,5 , 6-tetrahydropyrimidine, alkanolamine compounds such as triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, dimethylaminoethanol and 2- (N, N-dimethylaminoethoxy) ethanol, N, N ′ N "-tris (dialkylaminoalkyl) Hexahydrotriazines such as N, N ′, N ″ -tris (dimethylaminopropyl) -s-hexahydrotriazine, bis (dimethylaminoethyl) ether and metal salts such as iron, lead in the conventional oxidation state of metals, Inorganic and / or organic compounds of bismuth, zinc and / or tin, such as iron (II) chloride, iron (III) chloride, bismuth (III) bismuth (III) 2-ethylhexanoate, bismuth (III) octoate, bismuth (III) neodecanoate, zinc chloride, zinc 2-ethylcaproate, zinc (II) trifluoromethanesulfonate (zinc triflate), tin (II) octoate, tin (II) ethylcaproate, tin (II) palmitate, Dibutyltin (IV) dilaurate (DBTL), jib Rusuzu (IV) dichloride or lead octoate and the like.

  Preferred catalysts for use are tertiary amines, amidines and tin compounds and / or zinc compounds of the type mentioned. Particularly preferred catalysts are 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.0] nonene (DBN), 1,8-diazabicyclo [5.4.0]. ] Undec-7-ene (DBU) and dibutyltin (IV) dilaurate (DBTL) and zinc (II) trifluoromethanesulfonate (zinc triflate).

  The catalysts mentioned as examples above can be used individually in the reaction or in the form of any desired mixture, and beyond that, the total amount of catalyst used is based on the total amount of starting compounds used. Is used in an amount of 0.001 to 1.0% by weight, preferably 0.01 to 0.5% by weight.

  The progress of the reaction can be monitored, for example, by measuring the NCO content by titration means. When the desired NCO content is reached, the reaction is terminated.

  The silane-modified compound of formula (II) thus prepared (Z is derived from polyisocyanate (i)) is a low to high viscosity liquid, depending on the starting material selected, Clear, substantially colorless product having a residual level of monomeric starting diisocyanate of less than 1.0% by weight, preferably less than 0.5% by weight, more preferably less than 0.3% by weight, based on the total mass of the product Composing things.

  The still detectable NCO residue can be removed by adding methanol.

  In order to prevent premature crosslinking of the silane group of the compound of formula (II) during the preparation process of the invention, the addition of a water scavenger can be advantageous. For example, orthoformates such as triethyl orthoformate, vinyl silanes such as vinyl trimethoxysilane, or organophosphates such as dibutyl phosphate can be used. The water scavenger is used, if necessary, in an amount of up to 5% by weight, preferably up to 2% by weight, based on the total amount of starting material.

  If catalysts and / or water scavengers are used, they can be added to the starting compounds even before the start of the actual reaction. However, it is also possible to add these auxiliaries to the reaction mixture at any point during the reaction.

  In one preferred embodiment, the methods described herein are performed under an inert gas atmosphere such as, for example, nitrogen.

NCO-containing polyurethane prepolymer (ii)
In a further embodiment, the structural unit Y is a group derived from a prepolymer having an isocyanate group. This can in particular be a polyurethane prepolymer. Preparation of the polyurethane prepolymer Y-NCO with isocyanate groups according to the present invention requires the reaction of one or more of the above polyisocyanates with one or more polyols.

  The silane-modified compounds of formula (II) according to the invention in which Z is derived from an NCO-containing polyurethane prepolymer (ii) are prepared in principle in a manner known from polyurethane chemistry. In this case, the polyols (individually or as a mixture) may be reacted with an excess of polyisocyanates (individually or as a mixture) in the presence of catalysts and / or auxiliaries and adjuvants. The homogeneous reaction mixture is stirred until a constant NCO value is obtained. The unreacted polyisocyanate may then be removed by continuous distillation. The examples according to the invention describe prepolymers that are used further without further removal of the monomer polyisocyanate.

  In this continuous distillation process, only a partial amount of each prepolymer from the above process steps is exposed to high temperatures for a short time, while amounts that are not part of the distillation procedure remain at significantly lower temperatures. Understood to be a process. The elevated temperature in this case means the temperature necessary to evaporate the volatile components at a suitably selected pressure.

  The distillation is preferably carried out at a temperature of less than 170 ° C., more preferably 110 to 170 ° C., very preferably 125 to 145 ° C. and a pressure of less than 20 mbar, more preferably less than 10 mbar, very preferably 0.05 to 5 mbar. Is done.

  The temperature of the prepolymer-containing reaction mixture in an amount not yet included in the distillation procedure is preferably 0-60 ° C, more preferably 15-40 ° C, very particularly preferably 20-40 ° C.

  The temperature difference between the distillation temperature and the temperature of the prepolymer-containing reaction mixture in an amount not yet included in the distillation procedure is preferably at least 5 ° C, more preferably at least 15 ° C, very preferably 15-40 ° C. is there.

  Distillation is preferably carried out by exposing one volume increase of the prepolymer-containing reaction mixture for distillation to the distillation temperature for less than 10 minutes, more preferably less than 5 minutes, followed by active cooling if desired. It is carried out at such a rate that it brings the prepolymer-containing reaction mixture to the original temperature before distillation. The temperature load across in this case is preferably such that the temperature of the reaction mixture before distillation or the prepolymer after distillation is at least 5 ° C., more preferably at least 15 ° C., very preferably at least 15 than the distillation temperature used. ~ 40 ° C higher.

  Preferred continuous distillation techniques are short path, falling film and / or thin film distillation (see, for example, Chemische Technik, Wiley-VCH, Volume 1, 5th edition, pages 333-334).

  The preferred continuous distillation technique used is thin film distillation using the above parameters.

  The method for preparing the NCO-containing polyurethane prepolymer can be carried out without using a catalyst. The urethanization reaction may be accelerated using catalysts conventional in isocyanate chemistry. Suitable catalysts have already been described above for the preparation.

  Particularly preferred catalysts are 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,5-diazabicyclo [4.3.0] nonene (DBN), 1,8-diazabicyclo [5.4.0]. ] Undecene-7 (DBU) and dibutyltin (IV) dilaurate (DBTL).

The NCO-containing polyurethane prepolymer thus obtained is then reacted in the second step with the (secondary) formamidosilane OHC-HN-R ¹ -Si (R ² ) _n (OR ³ ) _3-n Can do. Reference is made here to the above process for preparing formamidosilane-modified polyisocyanates.

In an alternative regime, (secondary) formamidosilane OHC—HN—R ¹ —Si (R ² ) _n (OR ³ ) _3-n is first reacted with a polyisocyanate and only some of the isocyanate groups are reacted. Is also possible. The remaining isocyanate is then reacted with the polyol in a urethanization reaction in a second step. The reaction is carried out at a temperature of 20 to 200 ° C, preferably 40 to 160 ° C. The equivalent ratio of isocyanate groups to hydroxyl groups observed in this reaction is 0.7: 1 to 1.2: 1, preferably 0.8: 1 to 1.1: 1, more preferably 0.9: 1. A ratio of ˜1.05: 1.

Definitions of Preferred Substituents in Formula (I) and Formula (II) The following substituent definitions are preferred in formula (I) and formula (II), respectively: R ¹ is methylene (—CH ₂ —), ethylene or propylene ( in particular n- propylene, i.e. _-CH 2 _CH 2 CH ₂ - be); ^{R 2} and ^{R 3} independently of one another in each case, - methyl or - ethyl, preferably - methyl, n represents 0-2 It is an integer and n is preferably 0.

The following definitions of substituents are particularly preferred in formula (I) and formula (II) respectively: R ¹ is n-propylene; R ² and R ³ are in each case, independently of one another, -methyl or -ethyl N is an integer of 0-2.

Application and Substrate The coating material composition of the present invention is naturally used for coating a substrate. In particular, these compositions are used in automotive finishes, preferably in automotive OEM finishes.

  Usually, a two-component coating material is produced that is mixed immediately before painting. The intent thereby is in particular to prevent the possibility that silane reacts with OH groups and begins to hydrolyze.

  Automotive OEM finishes are conventionally done at room temperature and subsequently fired in the high temperature range (120-140 ° C.). The coating material composition of the present invention is preferably applied by electrostatic coating. In this method, both the vehicle body and the applied paint are electrostatically charged. Application in automotive plants is also routinely performed by robots with high speed rotating bells that produce very small droplets that then flow out as paint.

  However, it is also possible to use the coating material composition of the present invention for repair. This is typically done by gravity fed cup application with induced air followed by low temperature drying (room temperature up to 60 ° C. for 1-3 hours). A prerequisite for this is a more reactive coating material composition, which is reactive by, for example, more and more active catalysts, and by the use of silanol protecting groups (especially methoxy groups) that can be rapidly hydrolyzed. Can be increased.

  In addition, the coating material of the present invention can further be applied by conventional techniques to any of a wide variety of different substrates, such as spraying, rolling, knife coating, pouring, jetting, brushing, impregnation, dipping, or screens, Examples of suitable substrates that can be applied by printing techniques such as gravure, flexographic or offset printing, and also by transfer methods include wood, metal (especially known as wire, coil, can or container coating) Including metals used in) and even plastic (in the form of films, in particular ABS, AMMA, ASA, CA, CAB, EP, UF, CF, MF, MPF, PF, PAN, PA, PE, HDPE, LDPE, LLDPE, UHMWPE, PET, PMMA, PP, PS, SB, PUR PVC, RF, SAN, PBT, PPE, POM, PUR-RIM, SMC, BMC, PP-EPDM and UP (including DIN7728T1) and / or blocks and blends of these plastics, paper, leather, textiles, There are felt, glass, wood, woody material, cork, inorganic bonded substrates (such as wood boards and fiber cement boards), electronic assemblies or mineral substrates. Since thermosensitive substrates cannot be processed at high temperatures, curing in the low temperature range (room temperature to up to about 50 ° C. or 80 ° C.) is required, and as a result, a coating material composition having corresponding reactivity is required. Become.

  Substrates made of various of the above materials or already coated substrates can also be painted or finished. For example, to produce a film, it is possible to apply coating materials only temporarily to a substrate, and then partially or fully cure them and re-peel from them. The coating material according to the invention is particularly suitable for use in the finishing of automobiles, in particular automobile bodies or accessories, preferably in the form of clearcoat materials.

  The applied film thickness (before curing) is typically 0.5 to 5000 μm, preferably 5 to 1500 μm, more preferably 15 to 1000 μm.

  Suitable metal substrates can generally be made from all metals and metal alloys customary in the field. Preferably, metals such as aluminum, stainless steel, steel, titanium, ferrous metals and alloys of the kind conventionally used, for example in automobile construction, are used.

  The substrate is now typically pre-coated with an electrodeposition paint material, primer-surfacer (although also water-based or solvent-based-surface free) and basecoat materials, typically and usually. . When the coating material of the present invention is a colored top coating material, the application of the base coat may be omitted. It may be necessary or at least useful to pre-treat the surface of the target substrate by physical, chemical and / or physicochemical methods such as phosphating or polishing (in the case of repair).

  Furthermore, the target substrate can have a desired shape required for a particular application. This means that any three-dimensional substrate can be finished with the non-aqueous coating material composition according to the invention, in particular and preferably with an automobile body or parts thereof.

Experimental Section The following examples serve to illustrate the invention but should in no way be construed as imposing limitations on the scope of protection.

  All reported percentages are by weight unless otherwise specified.

  The NCO content was determined by titration according to DIN EN ISO 11909.

  The OH value was determined by titration method according to DIN 53240-2: 2007-11, and the acid value was determined by DIN36825. The reported OH content was calculated from the OH number determined by analysis.

  The residual monomer content was determined by DIN EN ISO 10283 by gas chromatography using an internal standard.

  The molecular weight is DIN 55672-1 (Gel Permeation Chromatography (GPC) -Part 1: Tetrahydrofuran (THF) as eluent) against polystyrene standards, modified to use a flow rate of 0.6 ml / min instead of 1.0 ml / min. ) By gel permeation chromatography.

  All viscosity measurements were performed according to DIN EN ISO 3219, using a Physica MCR 51 rheometer manufactured by Anton Paar Germany GmbH (Germany).

  Scratching: Scratching was tested on a complete system. For this purpose, the plate material was coated with a one-part aqueous OEM primer surfacer and a one-part OEM aqueous basecoat material before applying the clearcoat. The primer surfacer was baked at 165 ° C. for 20 minutes and the base coat was flashed off or pre-dried at 80 ° C. for 10 minutes. Next, a clear coat material was applied and baked at 140 ° C. for 30 minutes.

  Pendulum damping: Pendulum damping is measured on a glass plate according to DIN EN ISO 1522 and determined by Konig.

  Solvent resistance: For this purpose, a small amount of the relevant solvent (xylene, 1-methoxyprop-2-yl acetate, ethyl acetate or acetone) is placed in a test tube, a cotton pad is placed in the opening and the solvent is removed. A saturated atmosphere was developed in the test tube. The test tube was then brought onto the surface of the coating with a cotton pad and left there for 5 minutes. After wiping off the solvent, the film was examined for break / softening / adhesion loss (0 = no change, 5 = film break).

  Wet scratch resistance: Wet scratch resistance was tested according to DIN EN ISO 20556 using a laboratory cleaning unit. The number reported is the gloss loss in gloss units (GU) after scratching (10 cycles). Gloss was measured by reflectance measurements. The less gloss loss of GU, the more resistant the coating to wet scratching.

  Dry scratch resistance: The flat surface of a hammer (weight 800 g) was covered with steel wool or abrasive paper. A hammer was carefully applied at right angles to the coating and guided in orbit onto the coating without tipping over and without applying additional physical force. Ten back-and-forth strokes were made. Residual gloss was measured at three different locations transverse to the scratch direction. Gloss was measured by reflectance measurements. The less gloss loss of GU, the more resistant the coating to wet scratching.

[Synthesis Example]
Synthesis of secondary formamidosilane as precursor compound [Synthesis Example 1]
N- (3-trimethoxysilylpropyl) formamide A flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 1075.8 g (6 mol) of 3-aminopropyltrimethoxysilane at room temperature under a nitrogen atmosphere. Enter. While stirring, 378.6 g (6.3 mol) of methyl formate are added dropwise at a rate not exceeding 50 ° C. After the exotherm has ceased, stirring is continued for 4 hours at room temperature, and then excess methyl formate and the resulting methyl alcohol are distilled off under reduced pressure (0.1 mbar at 50 ° C.). Thereby, a colorless liquid having a viscosity of 11 mPa · s at 23 ° C. is obtained.

[Synthesis Example 2]
N- (3-methyldimethoxysilylpropyl) formamide 99.6 g (0.6 mol) of 3-aminopropylmethyldimethoxysilane at room temperature under a nitrogen atmosphere in a flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel Is charged. While stirring, 40.3 g (0.67 mol) of methyl formate are added dropwise at a rate not exceeding 50 ° C. After the exotherm has ceased, stirring is continued for 4 hours at room temperature, and then excess methyl formate and the resulting methyl alcohol are distilled off under reduced pressure (0.1 mbar at 50 ° C.). Thereby, a colorless liquid is obtained.

[Synthesis Example 3]
N- (3-triethoxysilylpropyl) formamide A flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 221.4 g (1 mol) of 3-aminopropyltriethoxysilane at room temperature in a nitrogen atmosphere. Enter. While stirring, 77.8 g (1.05 mol) of ethyl formate is added dropwise at a rate not exceeding 50 ° C. After the exotherm has ceased, stirring is continued for 4 hours at room temperature, then excess ethyl formate and the resulting ethyl alcohol are distilled off under reduced pressure (0.1 mbar at 80 ° C.). Thereby, a colorless liquid having a viscosity of 13 mPa · s at 23 ° C. is obtained.

[Synthesis Example 4]
N- (3-methyldiethoxysilylpropyl) formamide In a flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel, 497.9 g (2. 6 mol) is charged. While stirring, 212.1 g (2.8 mol) of ethyl formate is added dropwise at a rate not exceeding 50 ° C. After the exotherm has ceased, stirring is continued for 4 hours at room temperature, then excess ethyl formate and the resulting ethyl alcohol are distilled off under reduced pressure (0.1 mbar at 80 ° C.). Thereby, a colorless liquid having a viscosity of 12 mPas at 23 ° C. is obtained.

Synthesis of silane-modified compounds containing at least one tertiary formamidosilane group of general formula (I) or (II):
[Synthesis Example 5]
STP without NCO of formula (II)
In a nitrogen atmosphere, a flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 201.6 g (1.2 mol) of hexamethylene diisocyanate (HDI), and this initial charge was brought to 65 ° C. Heated. 54 mg of zinc trifluoromethanesulfonate was added and 248.8 g of N- (3-trimethoxysilylpropyl) formamide (1.2 mol, prepared according to Synthesis Example 1) was added dropwise at 65 ° C. over 75 minutes. Stirring was carried out at 65 ° C. for a total of 12.5 hours, and 54 mg of zinc trifluoromethanesulfonate was further added after 8 hours of stirring. At the end of the indicated stirring time, the concentration of free isocyanate groups was 11.1% (theoretical 11.2%). The reaction mixture was heated to 85 ° C. and 87.6 g (0.6 mol) of 2,2,4-trimethylpentane-1,3-diol was added at this temperature over 1 hour. After a stirring time of 3 hours at 85 ° C., the reaction mixture was admixed with 230.0 g of MPA to reduce the viscosity of the reaction mixture. According to IR, it was no longer possible to detect free NCO groups, so the reaction was terminated after stirring for a further 5.5 hours. This gives a clear liquid having a polymer content of 69% at 23 ° C. and a viscosity of 297 mPas.

  The amount of elemental Si in this formulation is 4.4% by weight and is a measure of the amount of crosslinkable trimethoxysilane groups it contains.

[Synthesis Example 6]
NCO-containing STP of formula (II)
In this synthesis example, the NCO group of Desmodur® N3900 was partially reacted with formamide silane. The resulting STP contains both NCO and silane groups and acts as a hybrid system (which means that it can crosslink not only through its NCO group but also through its silane group):
A flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 536.2 g of Desmodur® N3900 and 91 mg of zinc trifluoromethanesulfonate under a nitrogen atmosphere, and the initial charge was 100 ° C. Heated. At this temperature, 373.1 g of N- (3-trimethoxysilylpropyl) formamide (1.8 mol, prepared according to Synthesis Example 1) was added dropwise over 1 hour. Stirring was continued at 100 ° C. for a further 3 hours until the free NCO group content dropped to 4.8%. This batch was mixed with 114 g of butyl acetate and 114 g of solvent naphtha 100 and cooled to room temperature.

  This gave a clear liquid with a polymer content of 80% and a viscosity of 1030 mPas.

  The amount of elemental Si in this formulation is 4.4% by weight and is a measure of the amount of crosslinkable trimethoxysilane groups it contains.

[Synthesis Example 7]
Comparative Example to Synthesis Example 5-not the present invention STP without NCO of formula (II): 1-mercaptopropyl-3-trimethoxysilane instead of the (secondary) formamidosilane of the present invention in Synthesis Example 1 A flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 604.8 g (3.6 mol) of hexamethylene diisocyanate under a nitrogen atmosphere and the initial charge was heated to 85 ° C. did. At this temperature, 2,2.8-trimethyl-1,3-pentanediol (262.8 g / 1.8 mol) was added portionwise over 1 hour until the reaction mixture had an isocyanate group content of 17.1 wt%. Added. The reaction mixture was diluted with 230.0 g of 1-methoxy-2-propyl acetate (MPA) and adjusted to 55 ° C. First, at this temperature, 160 mg of 1,4-diazabicyclo [2.2.2] octane (DABCO) is added to the reaction mixture, followed by 3-mercaptopropyltrimethoxysilane 759 at a temperature of 50-55 ° C. .9 g (95%, 3.68 mol) was added to the reaction mixture. Stirring was continued at 50 ° C. for 4.5 hours until the isocyanate group content dropped to zero by IR spectroscopy. The batch was diluted with an additional 460 g of MPA. This gave a material with a polymer content of 68% by weight at 23 ° C. and a viscosity of 364 mPas.

  The amount of elemental Si in this formulation is 4.4% by weight and is a measure of the amount of crosslinkable trimethoxysilane groups it contains.

[Synthesis Example 8]
Comparative Example for Synthesis Example 6—NCO-Containing STP of Formula (II) According to the Invention: Use of 1-mercaptopropyl-3-trimethoxysilane in place of the (secondary) formamidosilane of Synthesis Example 1 of the present invention In this synthesis example, the NCO group of Desmodur® N3900 was partially reacted with mercaptosilane. The resulting STP contains both NCO and silane groups and acts as a hybrid system (which means that it can crosslink not only through its NCO group but also through its silane group):
A flask equipped with a thermometer, KPG stirrer, reflux condenser and dropping funnel was charged with 636.2 g of Desmodur® N3900 and 90 mg of 1,4-diazabicyclo [2.2.2] octane (DABCO) under a nitrogen atmosphere. The initial charge was heated to 82 ° C. At this temperature, 371.0 g (95%, 1.80 mol) of 3-mercaptopropyltrimethoxysilane was added dropwise over 1 hour. After this addition time, the batch was further stirred at 82 ° C. for 3 hours until the NCO group content dropped to 5.1 wt%. Thereafter, at a temperature of 82 ° C., 114 g of butyl acetate and 114 g of solvent naphtha were added and the batch was cooled to room temperature. This gave a silanized polyisocyanate having a polymer content of 80% by weight at 23 ° C. and a viscosity of 518 mPas.

  The amount of elemental Si in this formulation is 4.4% by weight and is a measure of the amount of crosslinkable trimethoxysilane groups it contains.

[Examples and Comparative Examples]
[Example and Comparative Example 1]
The STP of formula (II) prepared in Synthesis Example 5 was blended in the coating material composition of the present invention as follows, and compared with a composition containing no formamide silane having the same degree of crosslinking and the same resin solid content ratio. did. Since the comparative formulation does not contain silane groups, the catalyst (D) was also omitted.

Since the STP of Synthesis Example 5 no longer has free isocyanate groups, the test formulation is calculated so that the polyol (A) and the polyisocyanate (C) are crosslinked in equimolar amounts.

  The amount of flow control agent (E) added was selected so that the proportion of flow control agent present was the same based on the resin solids (solid content) of the total formulation.

  For example, Desmodur® N 3390 is supplied as a 90% solution in butyl acetate (BA).

  The coating material was prepared by mixing the binder with the remaining ingredients and stirring the mixture at room temperature. The spray viscosity was set using a 1: 1 mixture of 1-methoxyprop-2-yl acetate / solvent naphtha 100. The amount of solvent was selected so that the spray viscosity of Example 1 and Comparative Example 1 were the same. The spray viscosity setting is related to the flow time from the ISO cup, 5 mm nozzle (DIN EN ISO 2431) and is 30 seconds for this experiment and all further experiments.

  To examine the relevant performance characteristics, the formulations of Example 1 and Comparative Example 1 were tested alongside each other by the same procedure (application example from an automotive OEM finish).

The following table shows the results of the comparative performance test:

[Example 2 and Comparative Example 2]
The STP of the formula (II) prepared in Synthesis Example 6 is blended in the coating material composition of the present invention as follows, and the same degree of crosslinking and the same resin solid content as in Example 1 and Comparative Example 1. Compared to a composition containing no proportion of tertiary formamidosilane groups:

The test formulation was calculated such that polyol (A) and STP (B) and / or polyisocyanate (C) were crosslinked in equimolar amounts.

As in Example 1 and Comparative Example 1, paint samples were again produced and compared to each other by the method shown therein. The results are shown in the table below.

From the above table, it can be seen that the substrate coated with the coating material of the present invention containing a tertiary formamide silane group is significantly more resistant to various solvents than the comparative example containing no formamide silane modified compound of formula (II). It can also be seen that it also exhibits improved resistance and improved scratch resistance (dry and wet).

[Example 3 and Comparative Example 3]
The STP of formula (II) prepared in Synthesis Example 5 was formulated into the coating material composition of the present invention as follows and compared with the formulation containing STP of Synthesis Example 7. The formulation corresponds to Application Example 1 and Comparative Example 1. The STP of Synthesis Example 7 (Comparative Example) is a synthesis example, except that the silane group was introduced via 3-mercaptopropyltrimethoxysilane instead of via the secondary formamide silane described above. 5 is structurally equivalent to the STP of the present invention. Both formulations contain the same amount of crosslinkable silane groups (see figures for silane content in Synthesis Examples 5 and 7). The performance results obtained make it possible to compare the effect of STP based on the formamide silane component of the present invention against prior art silane components.

Since the STPs of Synthesis Examples 5 and 7 no longer have free isocyanate groups, the test formulation is calculated so that polyol (A) and polyisocyanate (C) are crosslinked in equimolar amounts. Otherwise, the procedure is as described in Example 1 and Comparative Example 1.

As in Example 1 and Comparative Example 1, paint samples were again produced and compared to each other by the method shown therein. The results are shown in the table below.

From the table above, the substrate coated with the coating material of the present invention shows somewhat improved wet scratch resistance compared to the comparative example consisting of mercaptosilane-containing STP, but in particular significantly less gloss. It can be seen that the dry scratch resistance is significantly improved, as can be confirmed from the loss. Moreover, since there is no longer any increase in pendulum damping, the hardness development with the coating of the present invention reached its end point more quickly than the coating formulation containing the comparative material.

[Application Example 4 and Comparative Example 4]
The isocyanate-containing STP of formula (II) prepared in Synthesis Example 6 was blended with the coating material composition of the present invention as follows and compared with the blend containing the isocyanate-containing STP of Synthesis Example 8. The formulation corresponds to Application Example 2 and Comparative Example 2. The STP of Synthesis Example 8 is the same as that of Synthesis Example 6 except that the silane group was introduced via 3-mercaptopropyltrimethoxysilane instead of via the formamide silane component of the present invention. It is structurally equivalent to STP. Both formulations contain the same amount of crosslinkable silane groups (see figures for silane content in Synthesis Examples 6 and 8). The performance results obtained make it possible to compare the effect of STP based on the formamide silane component of the present invention against prior art silane components.

The test formulation was calculated such that polyol (A) and STP (B) and / or polyisocyanate (C) were crosslinked in equimolar amounts.

As in Example 2 and Comparative Example 2, paint samples were again produced and compared to each other by the method shown therein. The results are shown in the table below.

From the above table, it can be seen that the substrate coated with the coating material of the present invention exhibits significantly improved hardness development compared to the comparative example consisting of mercaptosilane-containing STP. Further, it is obvious that the solvent resistance of Example 4 of the present invention is significantly improved as compared with Comparative Example 4.

Claims (15)

(A) at least one polyol (A);
(B) Formula (I);
Formula (I)

(In the formula (I):
X is an organic molecular residue, in particular an optionally substituted, linear or branched, aliphatic or alicyclic organic molecular residue;
R ¹ is an at least divalent, optionally substituted, linear or branched, aliphatic and / or alicyclic structural unit having ¹ to 12 carbon atoms, one or more non- Adjacent methylene groups can be replaced in each case by O or S;
R ² and R ³ are each independently, independently substituted, straight-chained or branched, aliphatic and / or alicyclic groups having 1 to 12 carbon atoms;
n is an integer of 0-2)
At least one tertiary formamidosilane-containing compound;
(C) one or more silane-free aliphatic or cycloaliphatic polyisocyanates optionally having free isocyanate groups or blocked isocyanate groups;
(D) at least one catalyst for crosslinking of the silane groups of component (B);
(E) optionally one or more flow control aids;
(F) optionally comprising one or more non-aqueous solvents,
At least one of the two components (B) and (C) necessarily contains free isocyanate groups or blocked isocyanate groups,
Non-aqueous coating material composition. Component (B) is represented by formula (II):
Formula (II):

(In the formula (II):
Z is a molecular residue consisting of (i) a polyisocyanate or (ii) an NCO-containing polyurethane prepolymer, and per molecule, at least one NCO group of the structure referred to in (i) or (ii) has the formula Modified with secondary formamide silane to form a compound of (II);
R ¹ , R ² , R ³ and n are as defined in claim 1)
The coating material composition according to claim 1, which is a tertiary formamidosilane-containing compound.   The coating material composition according to claim 2, wherein the tertiary formamide silane-containing component (B) is a polyurethane prepolymer containing no further free isocyanate groups or blocked NCO groups.   The tertiary formamide silane-containing component (B) is a polyurethane prepolymer comprising a polyurethane prepolymer based on hexamethylene diisocyanate (HDI) and a polyol, such as 2,2,4-trimethylpentane-1,3-diol, and the polyurethane 4. A coating material composition according to claim 2 or 3, wherein all NCO groups in the prepolymer are modified with a secondary formamide silane to form a compound of formula (II).   Component (B) is tetramethylene 1,4-diisocyanate, pentane 1,5-diisocyanate, hexamethylene 1,6-diisocyanate, 2,2,4-trimethylhexane 1,6-diisocyanate, ethylene diisocyanate, dodecane 1,12 From diisocyanates, 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate, IPDI) and mixtures of the above polyisocyanates, isomeric bis (4,4'-isocyanatocyclohexyl) methane and mixtures thereof A tertiary formamidosilane of formula I or II which is an aliphatic or cycloaliphatic, substituted or unsubstituted polyisocyanate reduced by at least one -NCO group, based on selected representatives, Coating according to claim 1 or 2, wherein the socyanate is present in each case as a monomer, dimer, trimer and / or polyisocyanate parent structure obtained by urethane, biuret, uretdione and / or allophanate formation. Material composition. (I) R ¹ is a divalent propylene group (—CH ₂ —CH ₂ —CH ₂ —),
R ³ is -methyl or -ethyl and n = 0; or (ii) R ¹ is a divalent propylene group (—CH ₂ —CH ₂ —CH ₂ —); or (iii) R ² and Each R ³ independently of one another is -methyl or -ethyl; or (iv) R ¹ is a divalent hexylene group (—CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ —),
The coating material composition according to any one of claims 1 to 5.   The tertiary formamidosilane-containing component (B) is 2.0 to 5.0, preferably 2.3 to 4.5, with an average NCO functionality of 5.0 to 50.0% by weight based on component (B). The coating material composition according to any one of claims 1, 2, 5, and 6, wherein the coating material composition has an isocyanate group content of 5.0 to 30.0% by weight.   The tertiary formamidosilane-containing component (B) is an aliphatic polyisocyanate resin based on hexamethylene diisocyanate (HDI) and is reduced by at least one —NCO group, in particular Desmodur® N3900. The coating material composition according to any one of claims 1, 2, 5, 6, and 7.   The coating material composition according to any one of claims 1 to 8, wherein the component (A) is a polyacrylate polyol.   The coating material composition according to any one of claims 1, 2, and 5 to 9, wherein component (B) contains blocked isocyanate groups or free isocyanate groups and component (C) is absent.   (I) Component (B) contains blocked isocyanate groups or free isocyanate groups, component (C) is present, or (ii) Component (B) contains neither blocked isocyanate groups nor free isocyanate groups First, the coating material composition according to any one of claims 1, 2 and 5 to 9, wherein component (C) is present.   The coating material composition according to any one of claims 1 to 9 and 11, comprising components (A), (B), (C), (D), (E) and (F).   Use of a coating material composition according to any one of claims 1 to 12 for the initial finishing of metal surfaces, plastics and composites, in particular automobile bodies or parts thereof.   An automotive clearcoat or topcoat material comprising the coating material composition according to one or more of claims 1-12.   A vehicle body or vehicle body part comprising the applied cross-linked coating material composition according to one or more of claims 1-12.